Valence regulation investigation of key factors on the electrochemical immobilization uranyl from wastewater

Electrochemical techniques are considered promising applications to immobilize uranium in alkaline wastewater in order to prevent its migration into groundwater and soil. In this work, the results of electrochemical and Atomic Force Microscope (AFM) demonstrate a successful immobilization of uranyl in the carbonate system by U(VI)-U(V), U(V)-U(IV) reduction, and U(V) disproportionation reactions. The results indicated that the electrochemical fixation rate in alkaline system could reach more than 99%. The valence state of uranium is the key factor affecting its migration in the working system. Where, the analysis of the immobilized samples by X-ray photoelectron spectroscopy (XPS) revealed that pHs, current density, and the presence of foreign cations significantly affect the valence state of uranium in the immobilized samples. Under same conditions, the reduction reactions of U(VI)-U(V) and U(V)-U(IV) occurred easily. Where, at pH higher than 3.4 or the current density in the range of 0.5–20 mA/cm2, high content of U(V) and U(IV) in the immobilized products was obtained. Other conditions favored the occurrence of the electrolytic water reaction, and the immobilized samples were dominated by U(VI). It was found that the temperature showed the greatest effect on the electrochemical immobilization rate. Where, the electrochemical immobilization rate increased by about 1.8 times when the ambient temperature increased from 293.15 to 328.15 K. This study provides a new idea for the immobilization of uranium in alkaline wastewater and demonstrates the feasibility of electrochemical immobilization of uranium in alkaline systems.